US7087780B2 - Process for producing tetrakis(Faryl)borate salts - Google Patents
Process for producing tetrakis(Faryl)borate salts Download PDFInfo
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- US7087780B2 US7087780B2 US10/877,026 US87702604A US7087780B2 US 7087780 B2 US7087780 B2 US 7087780B2 US 87702604 A US87702604 A US 87702604A US 7087780 B2 US7087780 B2 US 7087780B2
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- US
- United States
- Prior art keywords
- borate
- tetrakis
- aryl
- process according
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical class [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 38
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- -1 triarylmethyl tetrakis Chemical compound 0.000 claims abstract description 54
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 49
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical group C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 claims 3
- 125000005039 triarylmethyl group Chemical group 0.000 abstract description 11
- 150000001642 boronic acid derivatives Chemical group 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 150000001449 anionic compounds Chemical class 0.000 description 7
- 239000000306 component Substances 0.000 description 7
- 229910001412 inorganic anion Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 238000000844 transformation Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- GZEZIBFVJYNETN-PHDIDXHHSA-N (1r,2r)-1,2-dichlorocyclohexane Chemical compound Cl[C@@H]1CCCC[C@H]1Cl GZEZIBFVJYNETN-PHDIDXHHSA-N 0.000 description 1
- BLRPQFOUUPCTED-UHFFFAOYSA-N 1,1-dichloro-3,3-dimethylbutane Chemical compound CC(C)(C)CC(Cl)Cl BLRPQFOUUPCTED-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- WXYMNDFVLNUAIA-UHFFFAOYSA-N 1,8-dichlorooctane Chemical compound ClCCCCCCCCCl WXYMNDFVLNUAIA-UHFFFAOYSA-N 0.000 description 1
- PHHNNDKXQVKJEP-UHFFFAOYSA-N 1-bromo-5-chloropentane Chemical compound ClCCCCCBr PHHNNDKXQVKJEP-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- JEKYMVBQWWZVHO-UHFFFAOYSA-N 1-chloro-2,2-dimethylpropane Chemical compound CC(C)(C)CCl JEKYMVBQWWZVHO-UHFFFAOYSA-N 0.000 description 1
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- KKGUMGWNFARLSL-UHFFFAOYSA-N 3-(bromomethyl)pentane Chemical compound CCC(CC)CBr KKGUMGWNFARLSL-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- STJYMUBZVMSMBP-UHFFFAOYSA-N chlorocyclobutane Chemical compound ClC1CCC1 STJYMUBZVMSMBP-UHFFFAOYSA-N 0.000 description 1
- ZVTQWXCKQTUVPY-UHFFFAOYSA-N chloromethylcyclopropane Chemical compound ClCC1CC1 ZVTQWXCKQTUVPY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ITMSSZATZARZCA-UHFFFAOYSA-N n-ethyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CC)C1=CC=CC=C1 ITMSSZATZARZCA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FBOJNMRAZJRCNS-UHFFFAOYSA-M tetraethylphosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC FBOJNMRAZJRCNS-UHFFFAOYSA-M 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ILMKIFUAABITSV-UHFFFAOYSA-M tris(4-methylphenyl)sulfanium;bromide Chemical compound [Br-].C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ILMKIFUAABITSV-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
Definitions
- This invention relates to a method for making organic cation tetrakis( F aryl)borate salts from an alkali metal tetrakis( F aryl)borate.
- the organic cation is a protic ammonium cation or a triarylmethyl cation
- the tetrakis( F aryl)borate salt is useful as a cocatalyst for metallocene-catalyzed polymerization.
- the organic cation is an onium cation
- the tetrakis( F aryl)borate salt is useful as an initiator in the crosslinking of polyorganosiloxanes.
- alkali metal tetrakis( F aryl)borates are thermally sensitive. Alkali metal tetrakis( F aryl)borates are also sensitive to shock. These sensitivities clearly indicate potential hazards in the handling and processing of such compounds. Because alkali metal tetrakis( F aryl)borates are useful intermediates in the preparation of organic cation tetrakis( F aryl)borates, it would be very desirable to minimize or eliminate these sensitivity problems.
- An embodiment of this invention is a process for producing protic ammonium tetrakis( F aryl)borate, an onium tetrakis( F aryl)borate, or a triarylmethyl tetrakis( F aryl)borate from a solution or slurry of an alkali metal tetrakis( F aryl)borate in a liquid ethereal medium or liquid hydrocarbyl medium.
- This process comprises substituting the liquid ethereal medium or liquid hydrocarbyl medium with at least one halogenated hydrocarbon, without isolating the alkali metal tetrakis( F aryl)borate, to form a new slurry or solution.
- At least a portion of the new slurry or solution is mixed together with a salt selected from a) a protic ammonium salt, b) an onium salt, and c) a triarylmethyl salt, to produce a protic ammonium tetrakis( F aryl)borate, an onium tetrakis( F aryl)borate, or a triarylmethyl tetrakis( F aryl)borate.
- the triarylmethyl cation has three aryl groups bound to a central carbon atom.
- the protic ammonium cation has the formula [R 3 NH] ⁇ , in which each R is independently a hydrocarbyl group containing up to about thirty carbon atoms, and the onium cation has the formula [ER n ] ⁇ , wherein E is an element of any of Groups 15–17 of the Periodic Table, wherein each R is independently a hydrocarbyl group containing up to about thirty carbon atoms, and wherein n is equal to the valence of E plus one.
- E is an element of any of Groups 15–17 of the Periodic Table
- each R is independently a hydrocarbyl group containing up to about thirty carbon atoms
- n is equal to the valence of E plus one.
- the borate anion has four fluorine-containing aryl groups, each of which has bonded directly to an aromatic ring at least two fluorine atoms, or at least two perfluorohydrocarbyl groups, or at least one fluorine atom and at least one perfluorohydrocarbyl group. It is preferred that at least two fluorine atoms, or at least two perfluorohydrocarbyl groups are bonded directly to an aromatic ring. Each position on the aromatic ring(s) of the F aryl group that is not a fluorine atom or a perfluorohydrocarbyl group is substituted by a hydrogen atom, a hydrocarbyl group, an alkoxy group, or a silyl group.
- the F aryl groups may be the same or different from each other; it is preferred that all four F aryl groups are the same.
- Liquid ethereal medium is comprised of one or more liquid dihydrocarbyl ethers, and may also include one or more liquid hydrocarbons, water, or mixtures thereof.
- Liquid hydrocarbyl medium is comprised of one or more liquid hydrocarbons, and may also include one or more liquid dihydrocarbyl ethers, water, or mixtures thereof.
- the alkali metal tetrakis( F aryl)borate in a liquid ethereal medium is in the form of a solution
- alkali metal tetrakis( F aryl)borate in liquid hydrocarbyl medium is usually in the form of a slurry.
- the alkali metal tetrakis( F aryl)borate in liquid hydrocarbyl medium forms an oily layer at the bottom of the solution when traces of ether and/or water are present.
- the alkali metal tetrakis( F aryl)borate may be a lithium, sodium, potassium, rubidium, or cesium tetrakis( F aryl)borate.
- the alkali metal of the alkali metal tetrakis( F aryl)borate is lithium, potassium, or sodium; most preferably, the alkali metal is sodium or potassium. Most preferred as the alkali metal is potassium; thus, the most preferred alkali metal tetrakis( F aryl)borate is a potassium tetrakis( F aryl)borate.
- F aryl group shall be understood to mean, as described above, a fluorine-containing aryl group, which has bonded directly to an aromatic ring at least two fluorine atoms, or at least two perfluorohydrocarbyl groups, or at least one fluorine atom and at least one perfluorohydrocarbyl group. It is preferred that at least two fluorine atoms or at least two perfluorohydrocarbyl groups are bonded directly to an aromatic ring.
- Each position on the aromatic ring(s) of the F aryl group that is not a fluorine atom or a perfluorohydrocarbyl group is substituted by a hydrogen atom, a hydrocarbyl group, an alkoxy group, or a silyl group.
- the aromatic ring of the F aryl group may be, but is not limited to, benzene, naphthalene, anthracene, biphenyl, phenanthrene, or indene. Benzene is the preferred aromatic moiety.
- the perfluorohydrocarbyl groups include alkyl and aryl perfluorocarbons; suitable perfluorohydrocarbyl groups are, for example, trifluoromethyl, pentafluoroethyl, pentafluorophenyl, and heptafluoronaphthyl.
- the hydrocarbyl groups of the aryl groups are preferably C 1 to C 18 alkyl groups or C 6 to C 20 aryl or aralkyl groups.
- hydrocarbyl groups examples include methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, methylcyclohexyl, decyl, phenyl, tolyl, xylyl, benzyl, naphthyl, and tetrahydronaphthyl.
- the alkoxy groups preferably have C 1 to C 6 alkyl moieties. Some examples of alkoxy groups are methoxy, ethoxy, isopropoxy, methylcyclopentoxy, and cyclohexoxy.
- the silyl groups preferably have C 1 to C 18 alkyl groups or C 6 to C 20 aryl or aralkyl groups.
- Suitable silyl groups include trimethylsilyl, triisopropylsilyl, tert-butyl(dimethyl)silyl, tridecylsilyl, and triphenylsilyl.
- F aryl groups that may be present on the borate moiety in this invention include 3,5-bis(trifluoromethyl)phenyl, 2,4,6-tris(trifluoromethyl)-phenyl, 4-[tri(isopropyl)silyl]-tetrafluorophenyl, 4-[dimethyl(tert-butyl)silyl]-tetrafluorophenyl, 4′-(methoxy)-octafluorobiphenylyl, 2,3-bis(pentafluoroethyl)-naphthyl, 2-(isopropoxy)-hexafluoronaphthyl, 9,10-bis(heptafluoropropyl)-heptafluoroanth
- F aryl groups in which the all of the substituents are fluorine atoms.
- substituents are fluorine atoms.
- examples of such groups are pentafluorophenyl, 4-nonafluorobiphenylyl, 2-nonafluorobiphenylyl, 1-heptafluoronaphthyl, 2-heptafluoronaphthyl, 7-nonafluoroanthryl, 9-nonafluorophenanthryl, and analogous groups.
- the most highly preferred perfluoroaryl group is pentafluorophenyl; thus, the most highly preferred borate is tetrakis(pentafluorophenyl)borate.
- Halogenated hydrocarbons that may be used include, but are not limited to, dichloromethane, dibromomethane, trichloromethane, bromochloromethane, dichlorodifluoromethane, 1,2-dichloroethane, 1,2-dibromoethane, tetrachloroethane, 1-bromo-2-chloroethane, trichloroethylene, 1-bromopropane, (chloromethyl)cyclopropane, 1-bromobutane, 1-bromo-2-ethylbutane, 1,1-dichloro-3,3-dimethylbutane, cyclobutyl chloride, neopentyl chloride, 1-bromo-5-chloropentane, cyclopentyl bromide, 1,6-dibromohexane, trans-1,2-dichlorocyclohexane, 1-chloroheptane, 1,8-dich
- the substituting of the liquid ethereal medium or liquid hydrocarbyl medium, in which the alkali metal tetrakis( F aryl)borate is dissolved or slurried, with a halogenated hydrocarbon can be accomplished by a variety of means. Typical methods include decantation, solvent exchange via distillation (not to dryness), gentle evaporation (not to dryness), and centrifugation. For example, most of the liquid ethereal or hydrocarbyl medium may be decanted, followed by the addition of the halogenated hydrocarbon(s). If the two media are immiscible, they can be allowed to separate, so that more of the liquid ethereal or liquid hydrocarbyl medium can be decanted.
- the key is that the alkali metal tetrakis( F aryl)borate is not isolated from solvent at any point during the substitution. Generally, a slurry of the the alkali metal tetrakis( F aryl)borate in the halogenated hydrocarbon is formed.
- the substitution can be conducted at any suitable temperature below the boiling point of the halogenated hydrocarbon, so long as the alkali metal tetrakis( F aryl)borate is not adversely affected.
- the new slurry or solution comprising the alkali metal tetrakis( F aryl)borate in the halogenated hydrocarbon, is mixed with a triarylmethyl salt, protic ammonium salt, or onium salt.
- triarylmethyl cation refers to carbocations which have three aryl groups bound to a central carbon atom.
- the aryl groups of the triarylmethyl cation have from six to about twenty carbon atoms, can be the same or different, and can be substituted or unsubstituted.
- suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, and 2-ethylnaphthyl; preferred are tolyl and phenyl; most preferred is phenyl.
- the most preferred triarylmethyl cation is a triphenylmethyl cation.
- inorganic anions can be appropriate counterions for a triarylmethyl cation; examples of suitable inorganic anions include chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, and the like. Preferred inorganic anions are the halides, especially chloride; thus, the preferred salt is triphenylmethyl chloride.
- the halogenated hydrocarbon liquid medium is preferably dry (in the sense of having minimal water present), and it is preferred that the reaction is conducted in an inert atmosphere comprised of one or more inert gases, such as, for example, nitrogen, helium, or argon.
- Protic ammonium salts of the tetrakis( F aryl)borate can be formed from the alkali metal tetrakis( F aryl)borate.
- These ammonium cations have the general formula [R 3 NH] ⁇ , wherein each R is independently a hydrocarbyl group containing up to about thirty carbon atoms.
- R is preferably an aliphatic or aromatic hydrocarbyl group; preferred hydrocarbyl groups include methyl and phenyl.
- protic ammonium cations include, but are not limited to, trimethylammonium, triethylammonium, cyclohexyl(dimethyl)ammonium, tri(n-octyl)ammonium, phenyl(dimethyl)ammonium, diphenyl(ethyl)ammonium, and triphenylammonium cations.
- triarylmethyl salt many inorganic anions can be appropriate counterions for the protic ammonium cation.
- the halides, especially chloride are preferred inorganic anions; thus, the preferred salt is generally a protic ammonium chloride.
- the protic ammonium salt can be formed shortly before reacting it with the alkali metal tetrakis( F aryl)borate; this is accomplished by reacting R 3 N, wherein R is defined as for the protic ammonium cations, with a protic acid to form the protic ammonium cation.
- Preferred protic acids include hydrochloric acid, hydrobromic acid, hydroiodic acid, fluoboric acid, and hexafluorophosphoric acid; hydrochloric acid is a particularly preferred protic acid.
- the protic ammonium cation is formed in aqueous solution. For the mixing of the protic ammonium salt and alkali metal tetrakis( F aryl)borate, the exclusion of water is not necessary.
- onium salts can be reacted with the alkali metal tetrakis( F aryl)borate to yield the corresponding onium tetrakis( F aryl)borate.
- Onium cations are defined by the formula [ER n ] ⁇ , wherein E is an element of any of Groups 15–17 of the Periodic Table, each R is independently a hydrocarbyl group containing up to about thirty carbon atoms, and n is equal to the valence of E plus one. R is preferably an aliphatic or aromatic hydrocarbyl group. As an example of n, when E is sulfur, which has a valence of two, n is three.
- inorganic anions may be appropriate counterions for the onium cation.
- Preferred inorganic anions are the halides, especially chloride; thus, the preferred salt is generally an onium chloride.
- suitable onium salts include, but are not limited to, diphenyliodonium chloride, tris(p-tolyl)sulfonium bromide, and tetraethylphosphonium chloride.
- the alkali metal tetrakis( F aryl)borate and the triarylmethyl salt, protic ammonium salt, or onium salt are mixed together at room temperature.
- Mixing at room temperature is preferred because the yield of triarylmethyl, protic ammonium, or onium tetrakis( F aryl)borate is often much higher than when the mixture is heated. Some heat may be produced during the course of the reaction, raising the temperature of the mixture. The mixture may be heated, provided that the temperature does not exceed the thermal decomposition temperature of the product of the reaction.
- Heating during contacting of alkali metal tetrakis( F aryl)borate and the triarylmethyl, protic ammonium, or onium salt is preferred when a faster reaction rate is desired. Agitation of the reaction mixture is usually necessary for the reaction to proceed.
- the contact time for alkali metal tetrakis( F aryl)borate and the protic ammonium salt or onium salt is preferably from about fifteen minutes to about eight hours; more preferred is a time in the range of from about twenty minutes to about six hours.
- the contact time at room temperature is preferably in the range of from about twenty minutes to about twenty-four hours, and more preferably is in the range of from about one hour to about twelve hours.
- a contact time for alkali metal tetrakis( F aryl)borate and the triarylmethyl salt when heating in the range of from about thirty minutes to about twenty hours is preferred; a more preferable range is from about one hour to about fifteen hours; highly preferred is a contact time in the range of from about two hours to about twelve hours.
- reactants and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, a solvent, or etc.). It matters not what preliminary chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure.
- the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or in forming a mixture to be used in conducting a desired reaction.
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Abstract
Description
TABLE 1 | ||
Trial | Decomposed | Observations |
1 | Yes | Residue was mostly discolored (grey/black). No |
smoke or spark observed. | ||
2 | Yes | Small amount of smoke produced upon impact. |
Residue was completely discolored (gray/black). | ||
3 | Yes | Residue was completely discolored (grey/black). |
No smoke or spark observed. | ||
4 | Yes | Sparks and smoke observed upon impact. Black |
soot-like char residue. | ||
Claims (31)
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CN102149649A (en) * | 2008-08-08 | 2011-08-10 | 康宁股份有限公司 | Strengthened glass articles and methods of making |
RU2749716C2 (en) * | 2019-09-05 | 2021-06-16 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Catalyst activator for production of synthetic highly viscous base oils and method of preparation thereof |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US9738662B2 (en) | 2012-11-27 | 2017-08-22 | Albemarle Corporation | Process for producing tetrakis(F aryl)borate salts |
US9834569B2 (en) | 2012-11-27 | 2017-12-05 | Albemarle Corporation | Process for producing tetrakis(Faryl)borate salts |
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JP2006502200A (en) | 2006-01-19 |
EP1549656A1 (en) | 2005-07-06 |
US20040230075A1 (en) | 2004-11-18 |
ES2268442T3 (en) | 2007-03-16 |
EP1549656B1 (en) | 2006-07-12 |
DE60306791T2 (en) | 2007-07-12 |
ATE332904T1 (en) | 2006-08-15 |
US6831200B2 (en) | 2004-12-14 |
DE60306791D1 (en) | 2006-08-24 |
WO2004031197A1 (en) | 2004-04-15 |
US20040068134A1 (en) | 2004-04-08 |
JP4445865B2 (en) | 2010-04-07 |
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